Ethylene Furnace Coking

ABB Lummus Global – Training Tutorial

Coking
Part 1 of 3

Coking Tutorial, Page 1

This tutorial discusses the basic mechanisms of coking in

radiant coils. There are three parts to this tutorial. After
completing the first part, close this file and open Part 2
separately.

Separate tutorials are provided on:

♦ Coking Inhibition
♦ TLE fouling

Note: On many slides there is a reference number(s)

included in the center at the bottom. For example, slide 3
shows Ref 2, 13, 19. These numbers refer to the papers
listed in the literature list at the end of the tutorial.

TRA–ETH-002 Page 1 of 20
Ethylene Furnace Coking
ABB Lummus Global – Training Tutorial

Coke Formation

„Catalytic Coking
„Radical Coking
„Condensation Coking

Coking Tutorial Page 2

Radiant Coil Coking

The overall process of coking may be summarized as a

combination of three separate mechanisms:

♦ Catalytic
♦ Radical
♦ Tar Formation (Condensation)

Each mechanism is favored by different conditions and

produces a somewhat different type of coke. The formation
of the different types of coke are each favored during a
different phases of the furnace run length.

TRA–ETH-002 Page 2 of 20
Ethylene Furnace Coking
ABB Lummus Global – Training Tutorial

Catalytic Coking

„ Iron and nickel as well as their

oxides catalyze coking
„ Catalytic activity
y Ni >> Fe >> Cr > Ti
y NiO>Ni
y FeO > Fe > Fe2O3
„ Occurs between 350oC and 1050oC

Ref 2, 13, 19
Coking Tutorial Page 3

Catalytic coke, as the name implies, is catalyzed by

material in the radiant coil metallurgy. Ni and Fe
promote coking. Researchers have reported that the
combination of Ni and Fe is a far better catalyst than
either alone. Oxides of Ni and Fe are even stronger
promoters of coking.

This type of coking occurs in the form of filaments that

grow with the catalyst particle at the tip of the filament
or grow from a catalyst particle on the surface of the
tube. Other metals can catalyze coke but not nearly as
well as Ni and Fe.

TRA–ETH-002 Page 3 of 20
Ethylene Furnace Coking
ABB Lummus Global – Training Tutorial

Catalytic Coking

CxHy

(CxHy)
Radiant Coil Tube

Coking Tutorial Page 4

The process of catalytic coking is believed to proceed as

follows.

A reactive hydrocarbon is adsorbed onto the surface of a

catalyst particle. This process is called chemisorption.

TRA–ETH-002 Page 4 of 20
Ethylene Furnace Coking
ABB Lummus Global – Training Tutorial

Catalytic Coking

CxHy H2

(CxHy) yH + xC
Radiant Coil Tube

Coking Tutorial Page 5

The hydrocarbon decomposes to hydrogen and carbon

atoms. The hydrogen atoms can react to form hydrogen.

TRA–ETH-002 Page 5 of 20
Ethylene Furnace Coking
ABB Lummus Global – Training Tutorial

Catalytic Coking
CO + H2
CO
H2O
+
O+C C

Ref 10, 38, 41

Coking Tutorial Page 6

The carbon can follow one of many paths. It can:

♦ Be oxidized by the dilution steam

♦ React with oxygen atoms formed during decoking
process (during the decoking process, reactive oxygen
atoms from the steam and oxygen present become
temporarily bonded onto the tube surface
(chemisorbed))
♦ Remain on the surface as “encapsulated carbon”,
which is coke
♦ Diffuse through the metal matrix

TRA–ETH-002 Page 6 of 20
Ethylene Furnace Coking
ABB Lummus Global – Training Tutorial

Catalytic Coking
CO + H2
CO
H2O
+
O+C C

M7C3 C

M23C6 C

Ref 10, 38, 41

Coking Tutorial Page 7

As the carbon diffuses into the tube metal it can:

♦ React to carbides
♦ Deposit at the grain boundaries

When the carbon reacts to carbides, the type of carbide

will depend on the thermodynamic conditions and the
concentration of carbon. In areas of high carbon
concentration the carbide is usually M3C7 where M is
mostly Cr.

In areas of lower carbon concentrations, M23C6 is

favored.

TRA–ETH-002 Page 7 of 20
Ethylene Furnace Coking
ABB Lummus Global – Training Tutorial

Catalytic Coking
C

C C

Ref 1, 4, 10, 12, 13

Coking Tutorial Page 8

Free carbon that migrates to grain boundaries can

deposit and lift metal particles off the surface of the tube.

TRA–ETH-002 Page 8 of 20
Ethylene Furnace Coking
ABB Lummus Global – Training Tutorial

Catalytic Coking
C C
Cross section

Coking Tutorial Page 9

As carbon continues to deposit, a carbon filament forms

beneath the metal particle and the particle is lifted from
the surface. As long as the particle continues to catalyze
the decomposition of hydrocarbons more carbon is
formed and the filament continues to grow.

TRA–ETH-002 Page 9 of 20
Ethylene Furnace Coking
ABB Lummus Global – Training Tutorial

Catalytic Coking

Cross section

Coking Tutorial Page 10

Carbon is formed more rapidly than it can diffuse into

the surface so some carbon remains on the surface
reducing the area available for catalysis. When the
surface is completely covered with coke the catalysis stops
and the filament stops growing.

TRA–ETH-002 Page 10 of 20
Ethylene Furnace Coking
ABB Lummus Global – Training Tutorial

Catalytic Coking
20µm to 1.5mm thick layer

Filaments < 1 micron in diameter

Ref 1, 4, 10, 12, 13, 32

Coking Tutorial Page 11

The individual filaments formed by catalytic coking are

very small in size. Examinations of industrial furnace
tubes have shown catalytic coke layers ranging from a few
microns to 1.5 mm thick.

As the filaments grow from the surface, some catalyst

particles can be carried on the tip of the filament while
others can remain on the surface (See the red arrows).

The iron catalyst particles tend to fracture resulting in

branched filaments.

TRA–ETH-002 Page 11 of 20
Ethylene Furnace Coking
ABB Lummus Global – Training Tutorial

Catalytic Coking
„ For the growth of a single filament
y Rate controlling step is the diffusion of
carbon or the reaction rate
„ Overall coke formation
y Active surface sites
- Surface roughness
y Ni and Fe content of the alloy
y Surface conditions
- Oxides
- Sulfur
Ref 10, 19
Coking Tutorial Page 12

The rate-controlling step for the growth of a single

filament is believed to be the rate of diffusion of the carbon
through the particle or the rate of decomposition of the
hydrocarbon on the particle surface.

The overall rate of coke formation by catalytic coking is

controlled by the number of catalytic sites present on the
surface of the tube. An older, roughly surfaced tube has
more active sites and can therefore coke faster.

The presence of oxides and other compounds on the

surface of the tube can have a significant impact on
catalytic coking (see tutorial on Coke Inhibition)

TRA–ETH-002 Page 12 of 20
Ethylene Furnace Coking
ABB Lummus Global – Training Tutorial

Radical Surface Coking

Micro-species (MW < 100)
• Acetylene
• Ethylene
• Other olefins
• Butadiene
• Methyl, ethyl, phenyl, and Free radicals

benzyl free radicals

* * * * * *
Tube Surface

Ref 5, 32
Coking Tutorial Page 13

The second type of coking is radical surface coking. Radical

surface coke forms when light hydrocarbons in the vapor phase
react with radicals on the coke surface to add carbon and
produce new radicals. The catalytic coke deposited on the tube
surface acts as the initiation site for this form of coking.
Compounds in the gas, referred to as micro-species, react with
the free radicals on the coke surface. The micro-species
generally have molecular weights less than 100. Common
micro-species are:
♦ acetylene
♦ ethylene
♦ other olefins
♦ butadiene
♦ methyl, ethyl, phenyl, and benzyl free radicals.
Essentially all unsaturated molecules in the gas phase are
potential precursors of coke.

TRA–ETH-002 Page 13 of 20
Ethylene Furnace Coking
ABB Lummus Global – Training Tutorial

Radical Surface Coking

. +

Coke

Ref 31, 32
Coking Tutorial Page 14

A possible reaction of a gas phase micro-species (in this

case hexene) is shown in the following sequence of slides.

TRA–ETH-002 Page 14 of 20
Ethylene Furnace Coking
ABB Lummus Global – Training Tutorial

Radical Surface Coking

Coke

Coking Tutorial Page 15

The hexene undergoes initial reaction with the free

radical on the coke surface.

TRA–ETH-002 Page 15 of 20
Ethylene Furnace Coking
ABB Lummus Global – Training Tutorial

Radical Surface Coking

Beta scission

+ .
Coke

Coking Tutorial Page 16

Part of the hexene molecule is cleaved off via beta

scission.

TRA–ETH-002 Page 16 of 20
Ethylene Furnace Coking
ABB Lummus Global – Training Tutorial

Radical Surface Coking

Hydrogen abstraction

H
.
Coke

Coking Tutorial Page 17

A hydrogen atom is abstracted from the coke layer.

TRA–ETH-002 Page 17 of 20
Ethylene Furnace Coking
ABB Lummus Global – Training Tutorial

Radical Surface Coking

. + H2

Coke

Coking Tutorial Page 18

Another free radical is formed via this abstraction.

TRA–ETH-002 Page 18 of 20
Ethylene Furnace Coking
ABB Lummus Global – Training Tutorial

Radical Surface Coking

Dehydrogenation

H2

Coke

Coking Tutorial Page 19

Ring closure and dehydrogenation results.

TRA–ETH-002 Page 19 of 20
Ethylene Furnace Coking
ABB Lummus Global – Training Tutorial

Radical Surface Coking

k
P + C2 H 4 → 2C + P • + 2 H 2
•

dC
= 2 k C 2 H 4 C P • CC 2 H 4
dt
y Activity determined by gas composition
y Temperature
y Pressure
y Mass transfer

Ref 32
Coking Tutorial Page 20

The formation of radical coke is dependent on:

♦ The concentration of active sites on the coke surface

♦ The reaction rate of the micro-species with the surface
radicals
♦ The concentration of the micro-species in the gas phase

As a result the overall rate of radical coke formation is

influenced by:

♦ Temperature
♦ Pressure
♦ Mass transfer

This is the end of Part 1. Please close the file and open Part
2.

TRA–ETH-002 Page 20 of 20